Making a dispersion managing crystal

ABSTRACT

The present invention provides fluoride lens crystals for VUV optical lithography systems and processes. The invention provides a barium fluoride optical lithography crystal for utilization in 157 nm optical microlithography elements which manipulate below 193 nm optical lithography photons. The invention includes a barium fluoride crystalline material for use in dispersion management of below 160 nm optical lithography processes.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to the U.S. Provisional Patent Application Ser. No. 60/137,486, filed Jun. 4, 1999, entitled Lenses For Optical Systems, of Robert W. Sparrow, and U.S. Provisional Patent Application Ser. No. 60/180,886, filed Feb. 8, 2000, entitled Lenses For Optical Systems, of Robert W. Sparrow, and U.S. Provisional Patent Application Ser. No. 60/181,338 filed Feb. 9, 2000, entitled Lenses For Optical Systems, of Robert W. Sparrow, the content of which is relied upon and incorporated herein by reference in its entirety and the benefit of priority under 35 U.S.C. §120 is hereby claimed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to optical lithography, and particularly to optical microlithography crystals for use in optical photolithography systems utilizing vacuum ultraviolet light (VUV) wavelengths below 193 nm, preferably below 175 nm, more preferably below 164 nm, such as VUV projection lithography refractive systems utilizing wavelengths in the 157 nm region.

2. Technical Background

Semiconductor chips such as microprocessors and DRAM's are manufactured using a technology called “Optical Lithography”. An optical lithographic tool incorporates an illuminating lens system for illuminating a patterned mask, a light source and a projection lens system for creating an image of the mask pattern onto the silicon substrate.

The performance of semiconductors have been improved by reducing the feature sizes. This in turn has required improvement in the resolution of the optical lithographic tools. In general, the resolution of the transferred pattern is directly proportional to the numerical aperture of the lens system and inversely proportional to the wavelength of the illuminating light. In the early 1980's the wavelength of light used was 436 nm from the g-line of a mercury lamp. Subsequently the wavelength was reduced to 365 nm (I-line of mercury lamp) and currently the wavelength used in production is 248 nm obtained from the emission of a KrF laser. The next generation of lithography tools will change the light source to that of an ArF laser emitting at 193 nm. The natural progression for optical lithography would be to change the light source to that of a fluoride laser emitting at 157 nm. For each wavelength different materials are required to fabricate lenses. At 248 nm the optical material is fused silica. For 193 nm systems there will be a combination of fused silica and calcium fluoride lenses. At 157 nm fused silica does not transmit the laser radiation. At present the only material deemed to be useable at 157 nm is calcium fluoride. See, for example, Japanese unexamined Patent Publication No. 10-13 10 of Jan. 6, 1998 from Application No. 8153769 filed Jul. 14, 1996 and Japanese Patent No. 10-59799 Laid Open Mar. 3, 1998 based on an application filed Aug. 20, 1996, the Applicant in both cases being the NIKON Corporation.

Projection optical photolithography systems that utilize the vacuum ultraviolet wavelengths of light below 193 nm provide benefits in terms of achieving smaller feature dimensions. Such systems that utilize vacuum ultraviolet wavelengths in the 157 nm wavelength region have the potential of improving integrated circuits with smaller feature sizes. Current optical lithography systems used by the semiconductor industry in the manufacture of integrated circuits have progressed towards shorter wavelengths of light, such as the popular 248 nm and 193 nm wavelengths, but the commercial use and adoption of vacuum ultraviolet wavelengths below 193 nm, such as 157 nm has been hindered by the transmission nature of such vacuum ultraviolet wavelengths in the 157 nm region through optical materials. For the benefit of vacuum ultraviolet photolithography in the 157 nm region such as the emission spectrum VUV window of a F₂ excimer laser to be utilized in the manufacturing of integrated circuits there is a need for optical lithography crystals that have beneficial optical properties below 164 nm and at 157 nm.

The present invention overcomes problems in the prior art and provides a fluoride optical lithography crystal that can be used to improve the manufacturing of integrated circuits with vacuum ultraviolet wavelengths.

SUMMARY OF THE INVENTION

One aspect of the present invention is a below 160 nm optical lithography barium fluoride crystal. The barium fluoride crystal has a refractive index wavelength dispersion dn/dλ<−0.003 at 157 nm.

In another aspect, the present invention includes a dispersion management optical lithography crystal. The dispersion management crystal is an isotropic barium fluoride crystal. Preferably the barium fluoride crystal has a 157.6299 nm refractive index wavelength dispersion dn/dλ less than −0.003 and a 157.6299 nm refractive index n>1.56.

In a further aspect, the present invention includes a below 160 nm optical lithography method which comprises providing a below 160 nm optical lithography illumination laser, providing a calcium fluoride crystal optical element, providing a barium fluoride crystal optical element having a below 160 nm refractive index wavelength dispersion dn/dλ<−0.003, and transmitting the below 160 nm optical lithography light through the calcium fluoride optical element and the barium fluoride optical element to form an optical lithography pattern.

In another aspect, the present invention includes a method of making a dispersion managing optical lithography element. The method includes providing a barium fluoride source material, melting the barium fluoride source material to form a precrystalline barium fluoride melt, solidifying the barium fluoride melt into a barium fluoride crystal and annealing the barium fluoride crystal to provide an isotropic barium fluoride crystal with a 157 nm refractive index wavelength dispersion dn/dλ<−0.003

Additional features and advantages of the invention will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the invention as described herein, including the detailed description which follows and the claims.

It is to be understood that both the foregoing general description and the following detailed description are merely exemplary of the invention, and are intended to provide an overview of framework for understanding the nature and character of the invention as it is claimed.

Wherein reducing the wavelength of the illuminating light for lithography processes is necessary to achieve higher resolution, the illuminating light laser emission has a finite bandwidth. To achieve the resolution required at the 100 nm node, the optical lithography tool manufacturer using an all refractive optical design can either use a very highly line narrowed laser (to less than 2 pm) or can use two optical materials which have dispersion properties that compensate for the bandwidth of the laser.

In a preferred embodiment the invention includes providing isotropic optical lithography crystalline materials for color correction for VUV lithography in general but especially in the region of 157 nm to enable refractive lenses to be constructed to make use of the light from a fluoride excimer laser that has not been line narrowed to below 2 pm. The invention includes a range of fluoride crystalline materials that provide benefits to 157 nm optical lithography. In the preferred embodiment the dispersion managing optical lithography crystal is utilized in conjunction with a 157 nm optical lithography illumination laser with a bandwidth not less than 0.2 picometers.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The refractive index of a material varies with the wavelength of energy passing through it and this is called the dispersion of the material. Hence if light passing through a lens system, constructed of one optical material, has a range of wavelengths then each wavelength would be brought to a different focus so reducing resolution. This effect can be overcome by using a second optical material with different dispersion characteristics. This technique is known as color correction. To be of use as a color correction material, there are specific criteria that have to be met, namely the material must transmit at the wavelength of operation, it must be isotropic and must have optimum dispersion characteristics. At 157 nm, the only material that has had its dispersion characteristics measured to the necessary degree of accuracy is calcium fluoride. Applying the criteria of 157 nm transmission and of being isotropic, the following materials can be used as color correction materials.

I. Materials Based on Alkali Metal Fluorides

Lithium fluoride, sodium fluoride, potassium fluoride, and materials of the formula: MRF₃ in which M is either Li, Na or K and R is either Ca, Sr, Ba or Mg. Examples of such materials include but are not limited to: KMgF₃, KSrF₃, KBaF₃, KCaF₃, LiMgF₃, LiSrF₃, LiBaF₃, LiCaF₃, NaMgF₃, NaSrF₃, NaBaF₃, and NaCaF₃.

II. Materials Based on Alkaline Earth Metal Fluorides

Calcium fluoride, barium fluoride and strontium fluoride. Each of these materials can be combined with the other to form a mixed crystal of the formula (M1)_(x)(M2)_(1−x)F₂ in which M1 is either Ba, Ca or Sr and M2 is either Ba, Ca or Sr and x is an quantity between 0 and 1. Non-limiting examples are Ba_(0.5)Sr_(0.5)F₂ in which x=0.5 and Ba_(0.25)Sr_(0.75)F₂, in which x=0.75. When x=0, the materials are CaF₂, BaF₂, SrF₂

III. Materials Based on Mixed Crystals of the Formula M_(1−x)R_(x)F₂₊₁, in which M is either Ca, Ba or Sr and R is lanthanum.

In such materials the structure of the crystal is isotropic up to x values of 0.3. Examples of this formula include but are not limited to Ca_(0.72)La_(0.28)F_(2.28) in which x=0.28 or Ba_(0.74)La_(0.26)F_(2.26) in which x=0.26 or of the type Sr_(0.79)La_(0.21)F_(2.21) in which x=0.21.

Each of the above materials I, II and III can be manufactured using a technique known as the “Stockbarger” or “Bridgman” technique of crystal growth. This process comprises loading the powder of the material to be grown into a container known as a crucible. The crucible which usually is made of high purity graphite is positioned on a moveable support structure within a heater with sufficient power to raise the temperature to a level above the melting point of the material to be grown. After assembling the heater system around the crucible, the system is closed with a bell jar and evacuated using a combination of vacuum pumps. After a vacuum exceeding 10⁻⁵ Torr has been achieved, power is applied to the heater and is continually raised until a preset level has been achieved. This preset level of power is defined by melt trial runs. After a period of several hours at the melt power, the moveable support structure is activated and the crucible is made to slowly descend in the furnace. As the tip of the crucible descends, it cools and the molten material begins to freeze. By continuing the descent there is progressive solidification until all the melt is frozen. At this point, the power to the furnace is reduced to below the melt power, the crucible is raised back into the heater, allowed to reach thermal equilibrium over a period of several hours and then allowed to cool to room temperature by slowly reducing the power to the heaters. Once at room temperature, the vacuum is released, the bell jar removed followed by the heaters and the crystal can be removed from the crucible.

Although the Bridgman or Stockbarger method of crystal growth is the usual method of growing crystals of fluoride based materials, it is not the only method available. Techniques such as the Czochralski, Kyropoulos or Stober methods can also be utilized.

The size and shape of the disks resulting from these materials are variable e.g. for lenses: 118-250 mm in diameter by 30-50 mm in thickness. The disks are ground in a conventional manner to lenses of about the same dimensions and having the desired curvature. The lenses have a general application, for example, whenever color correction is required. The lenses can then be incorporated in a wide variety of optical systems, e.g. lasers including but limited to the 157 nm systems, spectrography systems, microscopes and telescopes.

The preceding specific embodiments are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

The entire disclosure of all applications, patents and publications, cited above and below, are hereby incorporated by reference.

From the foregoing description one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

The invention includes a below 160 nm optical crystal transmitting for use with a below 160 nm lithography laser having a bandwidth of at least 0.2 pm. The optical lithography crystal is comprised of an isotropic barium fluoride crystal which has a 157 nm transmission greater than 85% and a refractive index wavelength dispersion dn/dλ<−0.003 at 157 nm. Preferably the barium fluoride crystal has a 157 nm, refractive index wavelength dispersion dn/dλ<−0.004, and more preferably <−0.0043. Preferably the barium fluoride crystal has a 157 nm refractive index index n>1.56. More preferably n≧1.6, and most preferably n≧1.64. Preferably the barium fluoride crystal has a 157 nm refractive index temperature coefficient dn/dt>8×10⁻⁶/° C., and more preferably dn/dt≧8.5×10⁻⁶/° C. In a preferred embodiment the optical lithography barium fluoride crystal has a large dimension diameter >100 mm and a thickness >30 mm, and more preferably a diameter in the range of about 118 to 250 nm and a thickness in the range of about 30 to 50 mm. When utilized with a broadband width illumination source such as an F₂ excimer laser with a bandwidth of at least 0.5 pm, said barium fluoride crystal comprises a bandwidth dispersion managing optical element. Preferably the barium fluoride optical lithography crystal has a sodium contamination content <10 ppm by weight, more preferably <5 ppm by weight, and most preferably <1 ppm. Preferably the barium fluoride optical lithography crystal has a total rare earth contaminant content of less than 1 ppm by weight. Preferably the barium fluoride optical lithography crystal has a total oxygen contaminant content of less than 50 ppm by weight, and more preferably <20 ppm. Such low contaminant levels provide beneficial optical characteristics, and preferably the crystal has a 157 nm transmission ≧86%, and more preferably ≧88%.

In a further aspect the invention includes a below 160 nm dispersion management optical lithography crystal. The dispersion management optical lithography crystal comprises an isotropic barium fluoride crystal having a 157.6299 nm refractive index wavelength dispersion dn/dλ<−0.003 and a 157.6299 nm refractive index n>1.56. Preferably the dispersion management crystal's dn/dλ<−0.004, and more preferably dn/dλ<−0.0043. Preferably the crystal's refractive index n>1.6.

In a further aspect the invention includes a below 160 nm optical lithography method which includes providing a below 160 nm optical lithography illumination laser, providing a calcium fluoride crystal optical element, and providing a barium fluoride crystal optical element having a below 160 nm refractive index wavelength dispersion dn/dλ which is <−0.003. The method includes transmitting below 160 nm optical lithography light through the calcium fluoride optical element and the barium fluoride optical element to form an optical lithography pattern, preferably with feature dimensions ≦100 nm. Providing the barium fluoride crystal optical element preferably includes loading a barium fluoride crystal feedstock into a container, melting the feedstock to form a precrystallline barium fluoride melt, and progressively freezing the barium fluoride melt into a barium fluoride crystal. The method preferably further includes heating the barium fluoride crystal and slowly thermal equilibrium cooling the crystal and forming the barium fluoride crystal into an optical element. Preferably the illumination laser has a bandwidth ≧0.5 pm, and preferably ≧1 pm. In another aspect the invention includes the method of making a dispersion managing optical lithography element. The method includes providing a barium fluoride source material, melting the barium fluoride source material to form a precrystalline barium fluoride melt, solidfying the barium fluoride melt into a barium fluoride crystal, and annealing the barium fluoride crystal to provide an isotropic barium fluoride crystal with a 157 nm refractive index wavelength dispersion dn/dλ<−0.003. The method preferably includes providing a contaminant removing fluoride scavenger and melting the scavenger with the barium fluoride source material to remove contaminants. Preferably the scavenger is lead fluoride.

EXAMPLE

Barium fluoride optical lithography crystal samples were produced. 157 nm range refractive index measurements were made on a produced crystal. 157 nm range transmission exposures were made on a produced crystal.

Crystals were grown in high purity graphite crucible containers. High purity barium fluoride powder was loaded into the crucible. The loaded crucible was positioned on a movable support structure within a crystal growing heater device with sufficient power to raise the temperature to a temperature above 1280° C. The barium fluoride powder was melted above 1280° C. into a precrystalline barium fluoride melt, then the crucible was lowered through a 1280° C. containing thermal gradient to progressively freeze solidify the melt into a crystalline form. The formed crystal was then annealled by heating to a temperature below 1280° C. and then slowly cooling to allow the barium fluoride crystal to reach thermal equilibrium and reduce stress and birefringence of the crystal. Such formed barium fluoride crystal samples were then analyzed. A 157 nm transmission laser durability sample showed an external transmission of 86%. A 157 nm absolute refractive index sample showed a 157 nm dispersion at 20° C. of dn/dλ (157.6299)=−0.004376±0.000004 nm⁻¹ with the absolute refractive index at the 157 nm wavelength of 157.6299, n(λ=157.6299)=1.656690±0.000006, and also the refractive index temperature coefficient about 20° C. was found to be dn/dT (approx. 20° C., 1 atmosphere N₂)=10.6 (±0.5)×10⁻⁶/° C. and dn/dT (approx. 20° C., vacuum)=8.6(±0.5)×10⁻⁶/° C.

It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. 

What is claimed is:
 1. A method of making a dispersion managing optical lithography crystal for color correcting calcium fluoride at 157 nm, said method comprising: adding a first metal fluoride material and a second metal fluoride material sequentially to provide a mixed metal crystal fluoride color correction material, melting said mixed metal crystal fluoride color correction material to form a precystalline mixed metal crystal fluoride color correction material melt, solidifying said mixed metal crystal fluoride color correction material melt into a color correction material fluoride mixed crystal, annealing said color correction material fluoride mixed metal crystal to provide an isotropic color correction material fluoride mixed crystal with a 157 nm refractive index wavelength dispersion dn/dλ<−0.003 and a 157 nm transmission>80% wherein one of the metals of said mixed metal crystal is selected from the group consisting of Ca, Ba, Sr and Mg, and the other of said metals is a different metal selected from the group consisting of Ca, Ba, Sr, Mg, Li, K and La.
 2. A method as claimed in claim 1 wherein providing a mixed crystal fluoride material includes providing a mixed alkali metal fluoride and melting and solidifying said mixed alkali metal fluoride to provide a mixed alkali metal fluoride crystal having a MRF₃ formula with M chosen from a metal group consisting of Li, Na and K and R is chosen from a metal group consisting of Ca, Sr, Ba and Mg.
 3. A method as claimed in claim 1 wherein providing a mixed crystal fluoride material includes providing a mixed alkaline earth metal fluoride, and melting and solidifying said mixed alkaline earth metal fluoride to provide a mixed alkaline earth metal fluoride crystal having a (M1)_(x)(M2)_(1−x)F₂ formula with M1 chosen from a metal group consisting of Ba, Ca and Sr, M2 is chosen from the metal group consisting of Ba, Ca, Sr with M2 different than M1, and x is a number such that 0<x<1.
 4. A method as claimed in claim 1 wherein providing a mixed crystal fluoride material includes providing a mixed lanthanum metal fluoride and melting and solidifying said mixed lanthanum metal fluoride to provide a mixed lanthanum metal fluoride crystal having a M_(1−x)R_(x)F_(2+x) formula with M chosen from a metal group consisting of Ca, Ba and Sr, R is lanthanum, and x is a number such that 0<x<0.3. 